Stability insecticidal compositions and methods of making and using the same

This application is a National Stage Entry of PCT/US2020/064883, filed Dec. 14, 2020, which claims benefit of U.S. Provisional Application No. 62/947,377, filed Dec. 12, 2019, the disclosures of each of which are hereby incorporated by reference in their entirety.

The disclosure provides for agrochemical formulations capable of carrying high active ingredient loads and having improved stability. In another aspect, the disclosure provides for methods of making and using high-load agrochemical formulations having improved stability.

There is an ongoing need for agrochemical formulations that are more efficient and cost-effective.

By increasing the load of active agricultural ingredients in a formulation, application rates may be reduced, thereby streamlining application of agricultural chemicals to crops.

However, high-load formulations generally exhibit high accumulation rates of solids, which can lead to viscous mixtures that are difficult to mix, pump, or otherwise apply or distribute. Additionally, heat generation during milling is of concern for high-load agricultural formulations.

Long-term stability of high-load formulations is also a concern, generally. For example, high-load formulations are prone to sedimentation and syneresis or flocculation (i.e., the process of contact and adhesion whereby the particles of a dispersion form larger-size clusters). Suspension stabilization, such as stabilization of agrochemical compositions, is largely driven by polymer overlap and entropic loss. If the physical stability of a formulation is inadequate this can lead to the formation of hard packed or dilatant sedimentation layers that can be difficult to resuspend, making the product unusable for the end user.

In general, seed treatment formulations require a balance of properties, in particular there needs to be a balance between rheological structure which prevents sedimentation and viscosity which allows the product to be dispensed under moderate shear conditions.

Rheological measurements have been correlated with sedimentation and phase separation phenomena, and in particular yield stress is an excellent measure of rheological gel structure and sedimentation behavior. Yield stress is the amount of stress at which point a suspension experiences fluid-like behavior. Suspensions with increased yield stress resist sedimentation and thus, are more stable to sedimentation. See, for example, M. A. Faers, G. R. Kneebone, Pestic. Sci. 1999, 55, 312; see M. A. Faers, T. H. Choudhury, B. Lau, K. McAllister, P. F. Luckham, Colloids and Surfaces A: Physiochem. Eng. Aspects 2006, 288, 170; see J. L. Burns, Y. Yan, G. J. Jameson, S. Biggs, Colloids and Surfaces A: Physiochem. Eng. Aspects 2003, 214, 173; see Y. Yan, J. L. Burns, G. J. Jameson, S. Biggs, Chem. Eng. J. 2000, 80, 23; see M. A. Faers, Adv. Coll. Int. Sci. 2003, 106, 23.

The present inventors have found that formulations described herein not only achieve a high active ingredient load, but they also exhibit improved yield stress and thus improved stability.

The inventors of the present disclosure discovered it is possible to provide a stable, low-viscosity seed treatment suspension formulation comprising a high active ingredient load by adding glycol and/or glycerin to the formulation. In particular, the seed treatment suspension formulations of the invention exhibit a yield stress greater than that achievable by addition of conventional surfactants and xanthan gum. In some embodiments, the yield stress necessary to prevent sedimentation can be achieved at a lower viscosity. The inventors surprisingly found that glycols, such as propylene glycol, were highly effective in increasing yield stress while maintaining low viscosity in formulations containing high loads of active ingredients, such as neonicotinic pesticides. The inventors also surprisingly found the formulations described herein have a significantly lower syneresis compared to commercially available formulations over time (e.g., 1 year).

In some embodiments, the disclosure provides a seed treatment suspension formulation comprising a high load of active ingredient and a glycol and/or glycerin, wherein the seed treatment suspension formulation exhibits a yield stress greater than that achievable by addition of conventional surfactants and xanthan gum. In some embodiments, the yield stress necessary to prevent sedimentation can be achieved at a lower viscosity.

In some embodiments, the active ingredient is a pesticide, such as a neonicotinoid. In some embodiments, the neonicotinoid is selected from clothianidin and/or imidacloprid.

In some embodiments, the disclosure provides a seed treatment suspension formulation comprising:

The disclosure further provides a seed treatment suspension formulation comprising:

The disclosure further provides a seed treatment suspension formulation comprising:

The disclosure further provides a seed treatment suspension formulation comprising:

The disclosure further provides a seed treatment suspension formulation comprising:

The disclosure further provides for a method of producing an agrochemical formulation comprising:

The disclosure further provides for a method of increasing yield stress of an agricultural formulation, such as a seed treatment suspension, comprising adding a glycol, xanthan gum and/or glycerin to the seed treatment suspension formulation.

The disclosure further provides for a method of controlling insect pests comprising applying to a plant, plant part, seed, or habitat in which a plant is growing or to be grown a formulation comprising:

The disclosure also provides for seeds or plants or plant parts treated with compositions described herein.

The inventors of the present disclosure found that glycols, such as propylene glycol, and/or glycerin were highly effective in increasing yield stress while maintaining low viscosity in formulations containing high loads of active ingredients, such as neonicotinic pesticides. The inventors also unexpectedly found the formulations described herein have a significantly lower syneresis compared to commercially available formulations over time (e.g., 1 year). This is particularly surprising since highly loaded formulations are more prone to sedimentation and syneresis due to the higher solids content.

In some embodiments, the disclosure provides a seed treatment suspension formulation comprising a high load of an active ingredient and a glycol, wherein the seed treatment suspension formulation exhibits a yield stress equal to or greater than the yield stress of a formulation comprising less glycol and/or glycerin. In another embodiments, the disclosure provides a seed treatment suspension formulation comprising a high load of an active ingredient and a glycol, wherein the seed treatment suspension formulation exhibits a yield stress equal to or greater than the yield stress of a formulation without glycol and/or glycerin. In some embodiments, the seed treatment suspension formulation of the invention exhibits low viscosity (i.e., viscosity of the formulations is low enough to enable application of the formulation to seed using conventional means).

In an aspect, a seed treatment suspension formulation according to the present invention, the active ingredient can include at least one of any desired or known pesticide. In another aspect, the at least one pesticide is an insecticide, fungicide, herbicide, miticide, bactericide and/or microbicide.

In another aspect, the seed treatment suspension formulation of the invention includes one or more insecticidal active ingredients selected from the group consisting of acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, nithiazine, thiacloprid, thiamethoxam, ethiprole, fipronil, spiromesifen, beta-cyfluthrin, spirodiclofen, flubendiamide, thiodicarb, spirotetramat and a combination of clothianidin and a species ofand/or a product thereof.

In some embodiments, the species ofis selected from the group consisting ofstrain GB03,strain QST713.

In certain embodiments, the seed treatment suspension formulation of the invention comprises

In certain embodiments, the species ofor product thereof is present at a concentration of 10 to 10cfu/mL, or 10to 10cfu/mL, or 10to 10cfu/mL, or 10to 10cfu/mL

In certain embodiments, the at least one insecticidal active ingredient is one or more neonicotinoid.

In certain embodiments, the at least one insecticidal active ingredient is selected from acetamiprid, clothianidin, imidacloprid, nitenpyram, nithiazine, thiacloprid, thiamethoxam, or a combination thereof.

In certain embodiments, the at least one insecticidal active ingredient is present in the formulation at a concentration of over 600 g/L, at least about 625 g/L at least about 650 g/L, or of at least about 700 g/L, or of at least about 725 g/L, or of at least about 750 g/L.

In certain embodiments comprising two or more insecticidal agents, the insecticidal agents are present in the formulation at a combined (i.e., total) concentration of at least about 650 g/L, or of at least about 700 g/L, or of at least about 725 g/L, or of at least about 750 g/L. In an aspect, a first insecticidal agent may be present in an amount from about 1 g/L to about 250 g/L with the second or more insecticidal agent making up the difference, such that the total formulation comprises at least about 750 g/L, at least about 800 g/L, or at least about 900 g/L of insecticidal actives.

In certain embodiments, the at least one insecticidal active ingredient is present in the formulation at a concentration of about 650 g/L to about 1200 g/L, or about 700 g/L to about 1000 g/L, or about 725 g/L to about 900 g/L, or about 750 g/L to about 850 g/L.

In certain embodiments, the at least one insecticidal active ingredient is present in the formulation at a concentration of at least 50 w/w %, or at least 55 w/w %, or at least 60 w/w %, or at least 65 w/w %, or at least 70 w/w %. In certain embodiments, the at least insecticidal active ingredient is present in the formulation at a concentration of from about 50 w/w % to about 80 w/w %, or about 50 w/w % to about 70 w/w %, or about 50 w/w % to about 60 w/w %, or about 55 w/w % to about 80 w/w %, or about 55 w/w % to about 70 w/w %, or about 55 w/w % to about 65 w/w %, or about 55 w/w % to about 64% w/w %, or about 55 w/w % to about 63 w/w %, or about 55 w/w % to about 62 w/w %, or about 55 w/w % to about 61 w/w %, or about 55 w/w to about 60 w/w %, or about 56 w/w % to about 65%, or about 57 w/w % to about 65 w/w %, or about 58 w/w % to about 65 w/w %, or about 59 w/w % to about 65 w/w %, or about 60 w/w % to about 65 w/w %, or about 56 w/w % to about 60 w/w %, or about 57 w/w % to about 60%, or about 56 w/w % to about 59 w/w %, or about 58 w/w % to about 60.

In certain embodiments, the insecticidal active ingredient is clothianidin:

The International Union of Pure and Applied Chemistry (IUPAC) name for clothianidin is 1-(2-Chloro-1,3-thiazol-5-ylmethyl)-3-methyl-2-nitroguanidine.

In some embodiments, the seed treatment suspension formulation comprises:

In certain embodiments, the neonicotinoid is selected from clothianidin and/or imidicloprid.

In certain embodiments, the glycol is propylene glycol.

A seed treatment suspension formulation disclosed herein may optionally include one or more additional compounds providing an additional beneficial or otherwise useful effect. Such compounds include, without limitation, an adhesive, a surfactant, a solvent, a wetting agent, an emulsifying agent, a carrier, an adjuvant, a diluent, a dispersing agent, an insecticide, a pesticide, a fungicide, a fertilizer of a micronutrient or macronutrient nature, a herbicide, a feeding inhibitor, an insect molting inhibitor, an insect mating inhibitor, an insect maturation inhibitor, a nematacide, a nutritional or horticultural supplement, or any combination thereof.

In an aspect, a seed treatment suspension formulation according to the present invention may comprise one or more surfactants. In an aspect, any commercially available surfactant may be used. For example, Atlox 4913 is a surfactant provided by CRODA (see crodacropcare.com/en-gb/products-and-applications/product-finder/product/215/Atlox_1_4913), and Pluronic P-105 is a surfactant provided by BASF (see usbio.net/biochemicals/P4283). In certain embodiments, the one or more surfactants are each present in a concentration of from about 0.01 w/w % to about 10 w/w %, or from about 0.1 w/w % to about 7.5%, or from about 0.5% to about 5 w/w %, or from about 2 w/w % to 4 w/w %.

In an aspect, a seed treatment suspension formulation according to the present invention may comprise one or more wetting agents or dispersants. In an aspect, any commercially available wetting agent or dispersant may be used. For example, Morwet D-425 is a wetting agent/dispersant provided by AkzoNobel (see lema.com.mx/presentaciones/agroquimicos/Naph_Sulf_Jun14.pdf), and Soprophor 4d/384 is provided by Solvay Novecare (see solvay.com/en/product/soprophor-4d384). In certain embodiments, the one or more wetting agents are each present in the formulation at a concentration of about 0.01 w/w % to about 1 w/w %, or about 0.05 w/w % to about 0.8 w/w %, or about 0.025 w/w % to about 0.75 w/w %.

In an aspect, a seed treatment suspension formulation according to the present invention may comprise one or more antifoaming agents. In an aspect, any commercially available antifoaming agent may be used. For example, Antifoam 8830 FG is a 30% emulsion of polydimethylsiloxane formulated to control foam in both food and industrial processing, which is diluted with water or process liquids for addition to foam-generating solutions and which is capable of controlling foam over a broad pH range and in nonionic, cationic, and/or anionic systems. Antifoam 8830 FG, for example, is commercially available and provided by Harcros (see harcros.com/product/antifoam-8830-food-grade #).

In an aspect, a seed treatment suspension formulation according to the present invention may comprise one or more biocides. In an aspect, any commercially available biocide may be used. For example, Proxel GXL (20%) provided by Arch chemical (see excelind.co.in/Excel_Chemical/download/Proxel_GXL_literature.pdf), and Kathon CG/ICP is provided by DuPont (see dupont.com/products/kathoncgicp.html).

In an aspect, a seed treatment suspension formulation according to the present invention may comprise one or more antifreeze agent.

In an aspect, the one or more antifreeze agent may be any glycol. In certain embodiments, the antifreeze agent is propylene glycol.

In certain embodiments, the antifreeze agent is glycerin.

In certain embodiments, the one or more antifreeze agent is a glycol, glycerin, or a combination of one or more glycols and glycerin.

In certain embodiments, one or more glycols are each present in the formulation at a concentration of from about 0.1 w/w % to about 50 w/w %, or from about 0.5 w/w % to about 20 w/w %, about 1 w/w % to about 15 w/w %, or about 3 w/w % to about 10 w/w %.